US4283546A - 1,2,4-Triglycidyl triazolidines-3,5-diones and a process for the preparation thereof - Google Patents

1,2,4-Triglycidyl triazolidines-3,5-diones and a process for the preparation thereof Download PDF

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Publication number
US4283546A
US4283546A US06/182,110 US18211080A US4283546A US 4283546 A US4283546 A US 4283546A US 18211080 A US18211080 A US 18211080A US 4283546 A US4283546 A US 4283546A
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triazolidine
dione
epihalohydrin
reaction
hydrogen halide
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Ludwig Rottmaier
Rudolf Merten
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Bayer AG
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Bayer AG
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Assigned to BAYER AKTIENGESELLSCHAFT, A CORP. OF GERMANY reassignment BAYER AKTIENGESELLSCHAFT, A CORP. OF GERMANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: MERTEN RUDOLF, ROTTMAIER LUDWIG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3236—Heterocylic compounds
    • C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom

Definitions

  • This invention relates to new 1,2,4-triglycidyl triazolidine-3,5-diones corresponding to the following general formula: ##STR2## wherein R 1 , R 2 and R 3 , which may be the same or different, each represents hydrogen or methyl, preferably hydrogen.
  • the present 1,2,4-triglycidyl triazolidine-3,5-diones corresponding to above general formula (I) are obtained by reacting triazolidine-3,5-dione corresponding to the following formula: ##STR3## with an epihalohydrin or ⁇ -methyl halohydrin, such as epichlorohydrin, epibromohydrin or ⁇ -methyl epichlorohydrin, optionally in the presence of a suitable catalyst, or (with 1,3-dihalohydrin propane in the presence of hydrogen halide acceptors) using known methods and subsequently removing hydrogen halide by treatment with hydrogen halide acceptors.
  • an epihalohydrin or ⁇ -methyl halohydrin such as epichlorohydrin, epibromohydrin or ⁇ -methyl epichlorohydrin
  • 1,3-dihalohydrin propane propane in the presence of hydrogen halide acceptors
  • the triglycidyl triazolidine-3,5-diones may also be prepared in a single stage by reacting triazolidine-3,5-dione with an epihalohydrin or with 1,3-dihalohydrin propane in the presence of hydrogen halide acceptors, such as sodium or potassium hydroxide.
  • the triazolidine-3,5-dione used for preparing the new triglycidyl compounds corresponding to above general formula (I) is known and may be obtained, for example, by heating hydrazine-N,N'-dicarboxylic acid diamide to beyond 200° C. with elimination of ammonia.
  • a first-stage triazolidine-3,5-dione is reacted with an epihalohydrin in the presence of basic, acidic or neutral catalysts to form a halohydrin compound corresponding to the following general formula: ##STR4## wherein the radicals R independently represent radicals which may be converted into 1,2-epoxy ethyl radicals.
  • One such radical R which is capable of being converted into a 1,2-epoxy ethyl radical is, in particular, a hydroxy haloethyl radical carrying functional groups on various carbon atoms, such as the 2-chloro-1-hydroxy or 2-methyl-2-chloro-1-hydroxy ethyl radicals.
  • the catalysts preferably used for the addition of the halohydrin are tertiary amines and/or quaternary ammonium salts, such as trimethyl benzyl ammonium hydroxide, tetraethyl ammonium chloride, trimethyl benzyl ammonium chloride and trimethyl phenyl ammonium chloride; triethylamine, tri-n-butylamine, triethanolamine, N,N'-dimethylaniline, benzyl dimethylamine, pyridine, endoethylene piperazine and N,N'-dimethyl piperazine.
  • quaternary ammonium salts such as trimethyl benzyl ammonium hydroxide, tetraethyl ammonium chloride, trimethyl benzyl ammonium chloride and trimethyl phenyl ammonium chloride; triethylamine, tri-n-butylamine, triethanolamine, N,N'-dimethylaniline, benzyl dimethyl
  • Suitable catalysts are low molecular weight thioethers and/or sulphonium salts thereof, such as diethyl sulphide, dibenzyl sulphide, ⁇ -hydroxy ethyl ethyl sulphide, thiodiglycol and dibenzyl methyl sulphonium bromide and compounds which are capable of being converted into thioethers or sulphonium derivatives thereof by reaction with epihalohydrin, such as hydrogen sulphide, sodium sulphide or mercaptans.
  • alkali metal and alkaline earth metal salts such as lithium chloride and calcium thiocyanate.
  • the catalyst is preferably used in a quantity of from 0.01 to 5 mole percent, based on triazolidine-3,5-dione.
  • the halohydrin compound corresponding to above general formula (III) may also be obtained by reacting triazolidine-3,5-dione with a 1,3-dihalohydrin propane, such as 1,3-dichloro-2-propanol or 2-methyl-1,3-dichloro-2-propanol, in the presence of hydrogen halide acceptors, such as alkali metal or alkaline earth metal hydroxides, for example sodium and barium hydroxide, alkali metal or alkaline earth metal carbonates, for example, sodium carbonate and calcium carbonate, and tert.-amines, such as triethylamine.
  • a 1,3-dihalohydrin propane such as 1,3-dichloro-2-propanol or 2-methyl-1,3-dichloro-2-propanol
  • hydrogen halide acceptors such as alkali metal or alkaline earth metal hydroxides, for example sodium and barium hydroxide, alkali metal or alkaline earth metal carbonates
  • the reaction of the triazolidine-3,5-dione with the epihalohydrin is carried out using at least equivalent quantities of epihalohydrin, i.e. 1 mole of triazolidine-3,5-dione is reacted with at least 3 moles of epihalohydrin.
  • epihalohydrin i.e. 1 mole of triazolidine-3,5-dione is reacted with at least 3 moles of epihalohydrin.
  • the quantity of epihalohydrin will, of course, be kept as small as possible.
  • the reaction between triazolidine-3,5-dione and epihalohydrin is generally carried out at a temperature of from 20° to 200° C., preferably from 50° to 160° C., optionally under elevated pressure.
  • the reaction times are generally between 30 minutes and several days, although, in certain cases, they may be longer or shorter. Shorter reaction times are obtained by suitably selecting the reaction conditions, for example with regard to pressure.
  • reaction of the triazolidine-3,5-dione with the epihalohydrin or ⁇ -methyl halohydrin may even be carried out in the absence of catalysts, although higher temperatures and/or longer reaction times than indicated above are necessary in that case.
  • the halohydrin compound primarily the trichlorohydrin triazolidine-3,5-dione which may contain certain quantities of glycidyl compounds, depending on the excess of epihalohydrin or ⁇ -methyl halohydrin, is dehydrohalogenated in a second stage using hydrogen halide acceptors to form the 1,2,4-triglycidyl triazolidine-3,5-dione.
  • alkaline-reacting compounds used for removing hydrogen halide are, in particular, alkali metal or alkaline earth metal hydroxides, such as sodium hydroxide, potassium hydroxide and calcium hydroxide, preferably sodium hydroxide. It may be used in solid form or in solution, preferably in the form of from 20 to 50% by weight solutions.
  • Suitable hydrogen halide acceptors are alkali metal carbonates, particularly soda and potassium carbonate, in solid or dissolved form, alkali metal silicates, alkali metal phosphates, alkali metal aluminates and excess epihalohydrin or 1,2-alkylene oxides, such as ethylene oxide. Where epichlorohydrin is used, it is converted into glycerine dichlorohydrin.
  • the pH should preferably not exceed 13, more preferably not exceed 11. To achieve this, the alkali is gradually added or the solution is slowly added dropwise, the pH of the reaction mixture being controlled during the addition.
  • the elimination of hydrogen halide may be carried out at temperatures of from 20° to 120° C. Where the elimination of hydrogen halide is carried out using an alkali, for example potassium hydroxide, the reaction temperature should not exceed 70° C. if optimal yields are to be obtained. The best results are obtained at temperatures of from 30° to 35° C. Where alkali metal carbonates are used, however, the reaction temperature should be above 70° C., the maximum limit generally being imposed by the boiling point of the excess epihalohydrin.
  • an alkali for example potassium hydroxide
  • a water-immiscible organic solvent in order to be able to remove azeotropically the water formed during the reaction and the water added dropwise through the alkali solution.
  • the quantities of solvent added are not critical. Suitable solvents are chlorinated hydrocarbons, such as methylene chloride, chloroform, ethylene chloride or trichloroethylene. Where a large excess of epihalohydrin was used for the formation of the triazolidine-3,5-dione chlorohydrin compounds, the excess epihalohydrin may function as the water-immiscible solvent.
  • triazolidine-3,5-dione in a first stage, triazolidine-3,5-dione is reacted with epihalohydrin, preferably epichlorohydrin, in the presence of a catalyst, preferably a tertiary amine, a quaternary ammonium base, a quaternary ammonium salt or an organic sulphide or sulphonium salt, and, in a second stage, the halohydrin group-containing triazolidine-3,5-dione formed is treated with hydrogen halide acceptors, particularly alkali metal alkaline earth metal hydroxides or alkali metal carbonates in solid or dissolved form.
  • epihalohydrin preferably epichlorohydrin
  • the 1,2,4-triglycidyl triazolidine-3,5-diones are generally worked-up by removing the secondary product formed during the elimination of hydrogen halide, for example sodium chloride where sodium hydroxide is used as acid acceptor, by filtration under suction. Any residues of sodium chloride and alkali still present are removed by washing with water. However, all the sodium chloride and any alkali residues still present may, of course, also be directly removed by washing with water, i.e. without the preliminary step of filtration under suction.
  • hydrogen halide for example sodium chloride where sodium hydroxide is used as acid acceptor
  • the remaining solution which may first be dried over a suitable drying agent, such as anhydrous sodium sulphate, is then removed, optionally in vacuo, from the solvent, for example excess epichlorohydrin, which may be re-used in the following batches, and the pale-yellow to yellow coloured viscous oil obtained is crystallised by dissolution in suitable solvents, such as C 1 -C 4 alkanols, preferably methanol, ketones, such as butanone, glycol and diglycol monoethers or acetates thereof, such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether and ethylene glycol monomethyl ether acetate, followed by cooling.
  • suitable solvents such as C 1 -C 4 alkanols, preferably methanol, ketones, such as butanone, glycol and diglycol monoethers or acetates thereof, such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether and ethylene glycol monomethyl
  • the crystalline compound obtained a substantially pure triglycidyl triazolidine-3,5-dione, is filtered off under suction and may optionally be further purified by recrystallization, for example from methanol. In many cases, however, there is no need for purification, i.e. the crude product may be further processed as such.
  • the triglycidyl triazolidine-3,5-diones (crude product) obtained in accordance with the present invention have epoxide values of from 0.6 to 1.13, preferably from 0.85 to 1.13.
  • the "epoxide value” is to be understood to be the number of epoxide equivalents contained in 100 g of substance.
  • the “epoxide equivalent” is defined as the quantity of substance in grams which contains one 1,2-epoxide group.
  • One 1,2-epoxide group is equivalent to one mole of hydrogen halide.
  • the oligomeric products are formed during the production of 1,2,4-triglycidyl triazolidine-3,5-dione by reaction of active hydrogen atoms attached to nitrogen atoms of 1,2,4-triazolidine-3,5-dione, mono- or diglycidyl triazolidine-3,5-dione or mixtures thereof with 1,2-epoxide groups (glycidyl groups) of mono-, di- or triglycidyl triazolidine-3,5-dione or mixtures thereof and/or with the precursors of 1,2-epoxide groups, i.e. halohydrin groups.
  • the crude 1,2,4-triglycidyl triazolidine-3,5-dione may still contain saponifiable halogen (up to about 5% by weight of chlorine and up to about 13% by weight of bromine) which, if desired, may be further reacted with a hydrogen halide acceptor. All halogen may be practically removed, whereby an increasing epoxide value may be obtained.
  • the polyglycidyl compounds produced in accordance with the present invention may be used on their own or together with conventional hardeners, such as polyamines, polycarboxylic acids and anhydrides thereof, polyamidoamines, polyphenols, aminoplast and phenoplast resins, boron trifluoride complexes, etc, as impregnating agents for textiles, for example, fibres of polyesters, as coating compositions, for example for glass, metals and wood, as adhesives for plastics of various types, for example for bonding non-woven textile-like materials, and for the production of shaped articles, for example castings, pressings and laminates.
  • conventional hardeners such as polyamines, polycarboxylic acids and anhydrides thereof, polyamidoamines, polyphenols, aminoplast and phenoplast resins, boron trifluoride complexes, etc, as impregnating agents for textiles, for example, fibres of polyesters, as coating compositions, for example for glass, metals and wood, as adhesives
  • Example 2 40 kg of epichlorohydrin which was recovered from Example 2 are reacted with 4.04 kg of triazolidine-3,5-dione and 80 g of tetraethyl ammonium chloride in the same way as in Example 2.
  • Working-up in the same way gives 9.35 kg of a brownish oil which solidifies after a few hours and which has an epoxide value of 0.93 and a chlorine content of 3.1%.
  • test samples are prepared from which the following properties are obtained:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Epoxy Resins (AREA)
  • Epoxy Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US06/182,110 1979-09-01 1980-08-28 1,2,4-Triglycidyl triazolidines-3,5-diones and a process for the preparation thereof Expired - Lifetime US4283546A (en)

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DE19792935354 DE2935354A1 (de) 1979-09-01 1979-09-01 Triglycidyl-triazolidin-3,5-dione und verfahren zu ihrer herstellung
DE2935354 1979-09-01

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EP (1) EP0026312B1 (enrdf_load_stackoverflow)
JP (1) JPS5636484A (enrdf_load_stackoverflow)
DE (2) DE2935354A1 (enrdf_load_stackoverflow)
ZA (1) ZA805370B (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4467099A (en) * 1980-07-21 1984-08-21 Bayer Aktiengesellschaft Glycidyl-1,2,4-triazolidine-3,5-diones
EP0276506A1 (en) * 1987-01-16 1988-08-03 Agfa-Gevaert N.V. Image-receiving material for use in diffusion transfer reversal
US4801601A (en) * 1981-01-24 1989-01-31 Henkel Kommanditgesellschaft Auf Aktien N-substituted polyglycidyl urazole compounds, processes for their production and pharmaceutical preparations

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0043481B1 (de) * 1980-07-02 1984-11-28 Bayer Ag Semipermeable Membranen
DE3111238A1 (de) * 1981-03-21 1982-10-07 Bayer Ag, 5090 Leverkusen Substituierte triazolylmethyl-oxirane, verfahren zu ihrer herstellung sowie ihre verwendung als zwischenprodukte
DE3217875A1 (de) * 1982-05-12 1983-11-17 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von glycidyl-1,2,4-triazolidin-3,5-dionen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2708162A (en) * 1954-04-29 1955-05-10 Eastman Kodak Co Urazole stabilizer for emulsions sensitized with alkylene oxide polymers
DE1104965B (de) * 1958-06-19 1961-04-20 Knoll Ag Verfahren zur Herstellung von Derivaten des Urazols

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH471811A (de) * 1966-06-23 1969-04-30 Ciba Geigy Verfahren zur Herstellung von wasserlöslichen N,N'-Diglycidyl-Verbindungen
CH515925A (de) * 1968-11-21 1971-11-30 Ciba Geigy Ag Verfahren zur Herstellung neuer B-Methylglycidyl-isocyanurate und ihre Verwendung zur Herstellung härtbarer Massen
DD118641A1 (enrdf_load_stackoverflow) * 1975-04-10 1976-03-12

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2708162A (en) * 1954-04-29 1955-05-10 Eastman Kodak Co Urazole stabilizer for emulsions sensitized with alkylene oxide polymers
DE1104965B (de) * 1958-06-19 1961-04-20 Knoll Ag Verfahren zur Herstellung von Derivaten des Urazols

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4467099A (en) * 1980-07-21 1984-08-21 Bayer Aktiengesellschaft Glycidyl-1,2,4-triazolidine-3,5-diones
US4801601A (en) * 1981-01-24 1989-01-31 Henkel Kommanditgesellschaft Auf Aktien N-substituted polyglycidyl urazole compounds, processes for their production and pharmaceutical preparations
EP0276506A1 (en) * 1987-01-16 1988-08-03 Agfa-Gevaert N.V. Image-receiving material for use in diffusion transfer reversal

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EP0026312B1 (de) 1983-11-23
ZA805370B (en) 1981-09-30
JPS6338029B2 (enrdf_load_stackoverflow) 1988-07-28
EP0026312A1 (de) 1981-04-08
DE2935354A1 (de) 1981-03-19
JPS5636484A (en) 1981-04-09
DE3065685D1 (en) 1983-12-29

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